Controlling the identity of the tip-terminating atom or molecule in low-temperature atomic force microscopy has led to ground breaking progress in surface chemistry and nanotechnology. Lacking a comparative tip-performance assessment,...

With regard to the development of single atom catalysts (SACs), non-noble metal–organic layers combine a large functional variability with cost efficiency. Here, we characterize reacted layers of melamine and melem molecules on a Cu(111) surface by noncontact atomic force microscopy (nc-AFM), X-ray photoelectron spectroscopy (XPS) and ab initio simulations. Upon deposition on the substrate and subsequent heat treatments in ultrahigh vacuum (UHV), these precursors undergo a stepwise dehydrogenation. After full dehydrogenation of the amino groups, the molecular units lie flat and are strongly chemisorbed on the copper substrate. We observe a particularly extreme interaction of the dehydrogenated nitrogen atoms with single copper atoms located at intermolecular sites. In agreement with the nc-AFM measurements performed with an O-terminated copper tip on these triazine- and heptazine-based copper nitride structures, our ab initio simulations confirm a pronounced interaction of oxygen species at these N–Cu–N sites. To investigate the related functional properties of our samples regarding the oxygen reduction reaction (ORR), we developed an electrochemical setup for cyclic voltammetry experiments performed at ambient pressure within a drop of electrolyte in a controlled O2 or N2 environment. Both copper nitride structures show a robust activity in irreversibly catalyzing the reduction of oxygen. The activity is assigned to the intermolecular N–Cu–N sites of the triazine- and heptazine-based copper nitrides or corresponding oxygenated versions (N–CuO–N, N–CuO2–N). By combining nc-AFM characterization on the atomic scale with a direct electrochemical proof of performance, our work provides fundamental insights about active sites in a technologically highly relevant reaction.

AFM experiments at 78 K with an atomically defined O-terminated Cu tip allow determining bond lengths of an organic molecule with high precision.